EP0309221A2 - Elastomer-modifizierte Epoxydharze - Google Patents
Elastomer-modifizierte Epoxydharze Download PDFInfo
- Publication number
- EP0309221A2 EP0309221A2 EP88308756A EP88308756A EP0309221A2 EP 0309221 A2 EP0309221 A2 EP 0309221A2 EP 88308756 A EP88308756 A EP 88308756A EP 88308756 A EP88308756 A EP 88308756A EP 0309221 A2 EP0309221 A2 EP 0309221A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- acrylamide
- resin
- modifier
- mercapto
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- thermosetting polymers as matrices for reinforced structural composites is seriously limited by their brittleness and susceptibility to crack initiation and propagation.
- an epoxy resin is employed as the matrix for a fiberglass reinforced composite, high concentration of internal cracking occurs during cyclic load testing. Once initiated such cracks readily propagate along the fibers in regions of high fiber density.
- thermoplastics such as polyesters and polymethylmethacrylate have been enhanced by the addition of low concentrations of elastomeric polymers as small discrete particles suspended throughout the resin matrix.
- Butadiene nitrile rubbers with carboxyl groups at both ends of the chain, butadiene nitrile rubbers with terminal carboxyl groups as well as intermediate pendent carboxyl groups and butadiene nitrile rubbers which have no carboxyl groups but unsaturated carbon to carbon bonds interspersed along the chain were tested for impact modification of epoxy resins. It was found that only the carboxyl terminated polymers and the butadiene nitrile rubbers with intermediate pendent carboxyl groups provided toughening. See McGarry and Willner, "Crack Toughened Epoxy Resin Formulations" papers presented at the ACS 155th meeting, April 1968 at page 512.
- liquid polymer is disclosed in our U. S. Patent 4,529,558.
- This patent along with various related patents discloses a liquid heat curable polymer formed from rubber monomers such as isoprene or butadiene, acrylonitrile monomer and a potential acid catalyzed cure site monomer, N-(R-oxymethyl)acrylamide.
- rubber monomers such as isoprene or butadiene, acrylonitrile monomer and a potential acid catalyzed cure site monomer, N-(R-oxymethyl)acrylamide.
- This is a random terpolymer. It lacks any reactive carboxyl group as well as uniformly positioned reactive terminal groups. It is disclosed that these polymers can be used for preparation of gaskets when coated on a substrate such as metal, paper, cloth, nylon or the like. It is intended to be a solventless liquid heat curable polymer.
- an impact modified thermoset resin comprises either epoxy resin or epoxy novolak resin and an acrylamide diene nitrile random terpolymer which is dispersible in the resin at about less than 30°C, the acrylamide diene nitrile terpolymer being provided in an amount effective to provide impact modification of the thermosetting resin.
- an epoxy impact modifier is formed by reacting a prepolymer comprising 3 to 15% N-(R-oxymethyl) acrylamide; 60 to 80% diene monomer; 17 to 23% nitrile monomer selected from the group consisting of methacrylonitrile and acrylonitrile having a number average molecular weight effective to provide a liquid polymer at 20°C with a mercapto modifier said mercapto modifier selected from the group consisting of mercapto C3-C10 alkyl acids and C1-C10 alkyl ester derivatives thereof said composition formed by reacting said modifier with said polymer at less than about 175°C for time less than about 1 hour to provide a mercapto carboxyl modified prepolymer.
- liquid rubber formed from N-(R oxymethyl) acrylamide, diene, and nitrile is employed. This has been found to effectively impact modify epoxy and epoxy novolak thermoset resins.
- the epoxy resins or epoxy novolak resins are impact modified by the addition of liquid acrylamide diene nitrile rubber or prepolymer (hereinafter referred to as "ADN”.
- ADN liquid acrylamide diene nitrile rubber or prepolymer
- the ADN is formed by the prepolymerization of a diene (i.e., rubber forming) monomer such as isoprene, chloroprene, butadiene or alkyl esters of acrylic or methacrylic acid, a nitrile monomer such as acrylonitrile or methacrylonitrile and an N-(R-oxymethyl)acrylamide monomer or derivative thereof.
- a diene i.e., rubber forming
- the acrylamide monomers have the following general formula: R1 can be C3 to C22 alkyl, ether, aldehyde, ketone, amide, ester, carboxylic acid, imide or a phthalimide.
- N-(R-oxymethyl)acrylamides wherein R represents C3-C8 alkyl are commercially available.
- R1 must not be a group which will interfere with the chain transfer agent.
- R1 groups which are non-interfering can be derived from ketones, esters and ethers among others.
- Interfering R1 groups include those with pendent hydrogens which easily react with a radical such as the tertiary hydrogen in certain alcohols and alkyl amines or thiols.
- R1 can represent a phthalimide, preferably an N-alkyl phthalimide, so that the formed acrylamide monomer would have the following formula: wherein R3 is as C1 to about C10 alkyl and preferably has at least two carbon atoms and can optionally possess a pendent carboxyl group.
- R5 should be an alkylene group having from 1 to 8 carbon atoms.
- N-(isobutoxymethyl)acrylamide When N-(isobutoxymethyl)acrylamide is used as a starting material, approximately equimolar amounts of that compound and a replacement primary alcohol or monohydric thiol are reacted in the presence of an acid catalyst such as toluene sulfonic acid (for example, 0.5 weight percent based on the acrylamide monomer), at as low a temperature as possible.
- an acid catalyst such as toluene sulfonic acid (for example, 0.5 weight percent based on the acrylamide monomer)
- the isobutyl alcohol formed is vacuum distilled from the reaction mixture until the reaction has gone to completion. In a successful reaction, near theoretical amounts of isobutyl alcohol should be obtained. Excess replacement alcohols or thiols may be required to react all of the amide present to prevent formation of bisacrylamide cross-linking monomers.
- the ADN also contains an elasticizing or rubber monomer.
- rubber monomers include conjugated diolefins, such as isoprene, chloroprene and butadiene and certain esters of acrylic and methacrylic acid.
- any alkyl ester of acrylic acid having two to ten carbons in the alkyl group, and any alkyl ester of methacrylic acid with four to eight carbons in the alkyl group can be used.
- the ADN may optionally include 2-5% acrylic acid or methacrylic acid.
- the ADN is prepared by mixing from about 65% to about 71% rubber monomer, about 17-22% acrylonitrile or methacrylonitrile, and from about 7% to about 15% acrylamide as previously defined.
- the polymerization formulation should have various other components which are well known to those of ordinary skill in the polymer art. These would include a chain transfer agent, such as t-octyl mercaptan. Other such chain transfer agents include C6-C22 tertiary mercaptans.
- the amounts of rubber monomer, acrylonitrile or methacrylonitrile and acrylamide monomer may be varied to obtain the desired compatibility for the resin being modified.
- Suitable emulsifiers include fatty acid soaps and anionic sodium dodecylsulphate and commercially available emulsifiers, such as EMCOL 4910, the sodium salt of an unsymmetrical sulfosuccinate produced by Witco Chemical.
- Chelators such as disodium ethylene diamine tetraacetic acid are also helpful to remove any interfering metal impurities.
- Other components to initiate reaction or to increase the speed of the reaction would include a redox activator such as ferric chloride hexahydrate, a reducing agent such as sodium formaldehyde sulfoxylate and a free radical initiator.
- Suitable free radical initiators would include organic peroxides such as tert-butyl hydroperoxide, di-tertbutyl peroxide, cumene hydroperoxide, dicumene peroxide, benzoyl peroxide and the like.
- Organic peroxygen compounds such as tertbutyl peracetate, tertbutyl perbenzoate, di-tertbutyl perphthalate are also suitable.
- the ADN polymer is formed by combining the rubber monomer, the acrylonitrile or methacrylonitrile, and the acrylamide in the desired proportions within the limits set forth above, together with sufficient chain transfer agent, emulsifier, chelator, activator, reducing agent, free radical initiator and de-ionized air-free water (and optionally acrylic or methacrylic acid).
- the reactants are mixed and allowed to react for 2-24 hours at about 20°C. by which time yields of about 60-85% are obtained.
- the temperature of the reaction should be maintained at less than 40°C., preferably about 20°C.
- a sufficient amount of a regulator or chain transfer agent must be added to establish the molecular weight of the prepolymer low enough to maintain the desired viscosity.
- Suitable transfer agents or regulators include n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, as well as t-octyl mercaptan, the preferred chain transfer agent.
- the weight average molecular weight of the ADN should be established between about 10,000 and 30,000, and preferably, between 15,000 and 25,000.
- the amount of chain transfer agent required will vary depending on the precise monomer used and molecular weight desired, however, this will generally be less than about 5 weight percent based on the total weight of the monomers.
- the viscosity of the ADN desirably should be less than about 50,000 cps at a mixing temperature of 60°C., or between 90,000 and 150,000 cps at room temperature.
- this prepolymer can be further modified by the addition of a reactive mercapto acid modifier, i.e., R4-SH.
- a reactive mercapto acid modifier i.e., R4-SH.
- R4-SH a reactive mercapto acid modifier
- approximately 3-11 PHR of a mercapto (C3-C10) alkylene acid such as mercaptopropionic acid is added to the ADN.
- the mercapto group should preferentially react with the substituted acrylamide at the alkoxy methylene group under acid catalysis producing pendent carboxylic acid groups on the liquid rubber. This renders the liquid rubber more reactive with the epoxy resins.
- Suitable mercapto modifiers are esters of the mercaptoalkylene carboxylic acid.
- One particular ester is the tetra ester of pentaerythritol and four moles of mercapto propionic acid.
- Both the mercapto group and the acid or ester groups are potentially reactive with the ADN.
- these mercapto modifiers can act as cross-linking agents for the ADN.
- the thiol group is substantially more reactive than the acid or ester group. Therefore, the ADN is modified by the mercapto acid or ester by mixing the modifier with the ADN adding an acid catalyst, and heating the mixture to a temperature effective to cause the thiol group to react with the ADN (probably displacing the R-O-group on N-(R-oxymethyl) acrylamide).
- the reaction conditions are maintained sufficiently mild to enhance the reaction of the thiol group and limit or nearly eliminate the reaction of the carboxyl group.
- a ratio of about 0.2/1.0 to 1.0/1.0 of mercapto compound to acrylamide is preferred.
- an appreciable percentage of the acrylamide moieties in the ADN are usually not reacted.
- the ADN will be formed from the N-alkyl phthalimide in combination with isoprene and acrylonitrile.
- the preferred formulation includes 8-11% N[(2-phthalimidoethoxy)methyl]acrylamide, 65-71% isoprene and 21-23% acrylonitrile with a number average molecular weight of from about 5,000 to about 12,000.
- the ADN is used to modify epoxy resins and epoxy novolak resins.
- epoxy resins are the family of thermosetting resins containing the oxirane structure which is a three membered ring containing two carbon atoms and one oxygen atom. Originally, these were made by condensing epichlorohydrin and Bisphenol-A. Epoxy resins are generally formed now from low molecular weight diglycidyl ethers of Bisphenol-A and modifications thereof. Another type is formed by the oxidation of olefins with peracetic acid. Depending on molecular weight the resins range from liquids to solid resins. The present invention is limited to those which are liquid at less than 20°C.
- Epoxy-novolak resins are two step resins formed by reacting epichlorohydrin with phenol formaldehyde condensates. They are also defined as linear thermoplastic B-stage phenolic resins that are in a partial stage of cure. The epoxy-novolaks may have up to seven or more epoxy groups per molecule.
- Brand name resins include Epon 828, Epon 830, Epon 34, Dow DER 331, Epi-Rez 510, Epotuf 37-140 and Gen Epoxy 190.
- the ADN is mixed with the resin and prereacted to form partially prereacted ADN epoxy or epoxy novolak adduct concentrates which can then be cured with standard curing agents.
- 5-10 phr of the ADN is mixed with a strong acid catalyst such as para-toluene sulfonic acid or Alkaphos 3 (phosphoric acid partial ester) and heated to about 300°F (150°C) (.5-5 weight percent acid on liquid rubber), while stirring over a 5-15 minute period. Then sufficient resin is added to produce a 20-40 weight percent solution of the ADN in resin. This solution is further heated for 5-15 minutes at 300-400°F (150-205°C). This provides a clear stable ADN resin adduct which for use is mixed with additional resin to form an ADN content of 5-15 weight percent. The resin is then cured using standard curing mechanisms.
- a strong acid catalyst such as para-toluene sulfonic acid or Alkaphos 3 (phosphoric acid partial ester)
- 300°F 150°C
- Alkaphos 3 phosphoric acid partial ester
- epoxy resins were cured and tested in various ways. Certain physical data are set forth in the tables.
- Experiments 1, 5 and 9 represent unmodified Epon 828 cured with piperidine at 120°C.
- Experiments 2, 6, 10 and 11 demonstrate the use of prior art Kellogg, Kelpoxy 293-100 in Epon 828 acting as controls.
- Experiments 3, 4, 7, 8 and 12-16 and 18 represent the use of the novel liquid prepolymer in Epon 828.
- the chemical composition of the ADN was approximately as follows: isoprene 65%, acrylonitrile 21, HPMA 9%, isobutoxymethylacrylamide 3% and acrylamide 2%.
- the isobutoxymethylacrylamide and acrylamide are by products of the HPMA formation reaction.
- These ADN's have a number average molecular weight of from 6,000 to 9,000.
- compositions shown in tables 1 and 2 include 24 parts by weight Bisphenol A in Epon 828. This is reported to produce a bimodal distribution of phase dispersed particles of approximately 0.1-1.0 microns and 2 to 5 micron particles using Hycar 1300X8 liquid rubber products.
- the compositions in table 3 do not contain Bisphenol A and represent a more direct comparison of the relative efficacy of equal parts by weight of Hycar 1300X8 and the ADN of the present invention.
- control compositions 2 and 6 are replicates which contain 22 parts by weight Hycar brand liquid rubber based on epoxy resin while the experimental compositions 3, 4, 7 and 8 contain 10 parts by weight. Hence 2 and 6 would be expected to show dart impact strengths that are substantially greater than the values for experiments 3, 4, 7 and 8. The two values are in fact different by 30% and are lower than the blanks.
- the samples listed in Table 1 were tested according to the Gardner test procedure.
- the specimen size was 2.5 inch by 0.5 inch by 0.125 inches (6.357 cm X 1.27 cm X 0.3175 cm).
- the specimens were conditioned 48 hours at 70°F and 50% relative humidity and tested under these conditions.
- the epoxy compositions were cured in a 6.5 inch by 6.5 inch Teflon coated pan for 16 hours at 120°C in an air circulating oven to form 6.5 inch by 6.5 inch by 0.125 inch slabs which were cut into test pieces using a band saw. The results are the average from 10 test specimens.
- Epon 828-80.0 g Bisphenol A-19.2 g, ADN Liquid Rubber 89-8.0 g, piperidine-4.0 g, Alkaril Chemicals Alkaphos 3-0.20 g.
- Epon 828-80.0 g, Bisphenol A-19.2 g, ADN 28-02 8.0 g, piperidine-4.0 g, Alkaphos 0.20 g.
- the examples shown in table 3 were prepared by the Gardner test procedure with disc specimens of 1.33 inches diameter by 0.25 inch thickness. These specimens were conditioned for 48 hours at 70°F at 50% humidity and tested under these conditions.
- the epoxy compositions were cured in a 12 cavity Teflon coated, open mold with 1.33 inch diameter cavities for 16 hours at 120°C or using a staged cycle cure 1 hour at 80°C, 1 hour at 100°C, 16 hours at 120°C. Unless otherwise indicated, the 16 hour at 120°C cycle was used. The results again are the average of 10 to 12 test specimens.
- the ADN was modified with the thiol acid or ester listed and then added to the epoxy resin.
- the ADN was combined with a strong acid catalyst generally paratoluene sulfonic acid dissolved in alcohol.
- Cycat 4040 is 40% paratoluene sulfonic acid is isopropyl alcohol. This is mixed with the ADN at about 250-300°F for about 1-2 minutes. The alcohol is allowed to evaporate off and the acid catalyst ADN mixture is cooled to about room temperature.
- the thiol ester or acid is then added to this mixture and this mixture is heated to about 325°F for about 8 minutes and cooled.
- the modified ADN is then added to the epoxy resin as indicated.
- the ADN generally provides comparable results to the Hycar liquid rubber when simply added with the epoxy resin and cured with an acid catalyst.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US99253 | 1979-12-03 | ||
US07/099,253 US4812521A (en) | 1987-09-21 | 1987-09-21 | Epoxy resins modified with N-R-[(oxy or thio)methyl]acrylamide terpolymers |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0309221A2 true EP0309221A2 (de) | 1989-03-29 |
EP0309221A3 EP0309221A3 (de) | 1990-04-18 |
Family
ID=22273925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88308756A Withdrawn EP0309221A3 (de) | 1987-09-21 | 1988-09-21 | Elastomer-modifizierte Epoxydharze |
Country Status (5)
Country | Link |
---|---|
US (1) | US4812521A (de) |
EP (1) | EP0309221A3 (de) |
JP (1) | JPH01108251A (de) |
AU (1) | AU601930B2 (de) |
CA (1) | CA1337092C (de) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0570611A1 (de) * | 1992-05-20 | 1993-11-24 | Friedrich Maurer Söhne GmbH & Co. KG | Überbrückungskonstruktion für Dehnungsfugen |
WO2010108723A1 (de) | 2009-03-24 | 2010-09-30 | Evonik Degussa Gmbh | Prepregs und daraus bei niedriger temperatur hergestellte formkörper |
WO2010108701A1 (de) | 2009-03-24 | 2010-09-30 | Evonik Degussa Gmbh | Prepregs und daraus hergestellte formkörper |
DE102010029355A1 (de) | 2010-05-27 | 2011-12-01 | Evonik Degussa Gmbh | Verfahren zur Herstellung von lagerstabilen Polyurethan-Prepregs und daraus hergestellte Formkörper |
DE102010041247A1 (de) | 2010-09-23 | 2012-03-29 | Evonik Degussa Gmbh | Verfahren zur Herstellung von lagerstabilen Polyurethan-Prepregs und daraus hergestellte Formkörper aus Polyurethanzusammensetzung in Lösung |
WO2012093006A1 (de) | 2011-01-04 | 2012-07-12 | Evonik Degussa Gmbh | Composite-halbzeuge und daraus hergestellte formteile sowie direkt hergestellte formteile auf basis von hydroxyfunktionalisierten (meth) acrylaten, die mittels uretdionen duroplastisch vernetzt werden |
DE102011006163A1 (de) | 2011-03-25 | 2012-09-27 | Evonik Degussa Gmbh | Lagerstabile Polyurethan-Prepregs und daraus hergestellte Formkörper aus Polyurethanzusammensetzung mit flüssigen Harzkomponenten |
DE102011087226A1 (de) | 2011-11-28 | 2013-05-29 | Evonik Degussa Gmbh | Pseudo-thermoplastische, selbstvernetzende Composites |
DE102013204124A1 (de) | 2013-03-11 | 2014-09-11 | Evonik Industries Ag | Composite-Halbzeuge und daraus hergestellte Formteile sowie direkt hergestellte Formteile auf Basis von hydroxyfunktionalisierten (Meth)Acrylaten und Uretdionen die mittels Strahlung duroplastisch vernetzt werden |
WO2015074887A1 (de) | 2013-11-19 | 2015-05-28 | Evonik Industries Ag | Formteile auf basis von dien-funktionalisierten (meth)acrylaten und (hetero-)diels-alder-dienophilen, mit reversibler vernetzung |
DE102014207785A1 (de) | 2014-04-25 | 2015-10-29 | Evonik Degussa Gmbh | Verfahren zur Herstellung von lagerstabilen Epoxy-Prepregs und daraus hergestellte Composites auf Basis von radikalisch polymerisierbaren Säuren und Epoxiden |
EP2979851A1 (de) | 2014-07-28 | 2016-02-03 | Evonik Degussa GmbH | Effiziente Herstellung von Composite-Halbzeugen und -Bauteilen im Nasspressverfahren unter Einsatz von hydroxyfunktionalisierten (Meth) Acrylaten, die mittels Isocyanaten oder Uretdionen duroplastisch vernetzt werden |
EP2982704A1 (de) | 2014-08-06 | 2016-02-10 | Evonik Degussa GmbH | Reversibel vernetzte Polymeremulsionen |
EP2993202A1 (de) | 2014-09-08 | 2016-03-09 | Evonik Degussa GmbH | Composite-Halbzeuge und daraus hergestellte Formteile sowie direkt hergestellte Formteile auf Basis von hydroxyfunktionalisierten (Meth)Acrylaten und Uretdionen, die duroplastisch vernetzt werden |
EP3199575A1 (de) | 2016-01-29 | 2017-08-02 | Evonik Degussa GmbH | Neuartiger hetero-diels-alder-vernetzer und deren verwendung in reversibel vernetzenden polymersystemen |
EP3296347A1 (de) | 2016-09-20 | 2018-03-21 | Evonik Degussa GmbH | Neuartiger dien-baustein für die verwendung in reversibel vernetzenden (hetero-)diels-alder-polymersystemen |
WO2018054684A1 (de) | 2016-09-20 | 2018-03-29 | Evonik Degussa Gmbh | Neuartiger vernetzer-baustein für die verwendung in reversibel vernetzenden polymersystemen |
EP3330311A1 (de) | 2016-12-02 | 2018-06-06 | Evonik Degussa GmbH | Lagerstabile 1k-polyurethan-prepregs und daraus hergestellte formkörper aus polyurethanzusammensetzung |
EP3560971A1 (de) | 2018-04-27 | 2019-10-30 | Evonik Degussa GmbH | Zweikomponentige hybrid-matrix-system aus polyurethanen und polymethacrylaten zur herstellung von kurzfaserverstärkten halbzeugen |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4315866B2 (ja) * | 2004-06-29 | 2009-08-19 | 横浜ゴム株式会社 | 硬化性エポキシ樹脂組成物 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4529558A (en) * | 1983-01-21 | 1985-07-16 | Eagle-Picher Industries, Inc. | Heat curable solventless liquid prepolymer |
EP0285898A2 (de) * | 1987-04-04 | 1988-10-12 | Bayer Ag | Zubereitungen und Verfahren zum Zurichten von Leder und zur Textilbeschichtung |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3551471A (en) * | 1968-05-22 | 1970-12-29 | Goodrich Co B F | Liquid hydroxy terminated polymers of butadiene-acrylonitrile |
US4232135A (en) * | 1978-01-10 | 1980-11-04 | Imperial Chemical Industries Limited | Coating compositions |
EP0038127B1 (de) * | 1980-04-14 | 1984-10-17 | Imperial Chemical Industries Plc | Mehrschichtiges Überzugsverfahren unter Verwendung eines wässerigen thixotropen Grundschichtgemisches, das vernetzte Polymerpartikeln aufweist |
US4562008A (en) * | 1983-01-21 | 1985-12-31 | Eagle-Picher Industries, Inc. | Heat curable solventless liquid prepolymer and novel monomer derived from hexylcarbitol for use therewith |
US4515849A (en) * | 1983-06-01 | 1985-05-07 | Matsui Shikiso Chemical Co. Ltd. | Transfer printing sheet, printing method and printed article |
US4681811A (en) * | 1985-08-19 | 1987-07-21 | Ppg Industries, Inc. | Color plus clear coatings employing polyepoxides and polyacid curing agents in the clear coat |
US4650718A (en) * | 1985-08-19 | 1987-03-17 | Ppg Industries, Inc. | Color plus clear coatings employing polyepoxides and polyacid curing agents |
-
1987
- 1987-09-21 US US07/099,253 patent/US4812521A/en not_active Expired - Fee Related
-
1988
- 1988-08-24 CA CA000575516A patent/CA1337092C/en not_active Expired - Fee Related
- 1988-09-20 JP JP63233885A patent/JPH01108251A/ja active Pending
- 1988-09-20 AU AU22412/88A patent/AU601930B2/en not_active Ceased
- 1988-09-21 EP EP88308756A patent/EP0309221A3/de not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4529558A (en) * | 1983-01-21 | 1985-07-16 | Eagle-Picher Industries, Inc. | Heat curable solventless liquid prepolymer |
EP0285898A2 (de) * | 1987-04-04 | 1988-10-12 | Bayer Ag | Zubereitungen und Verfahren zum Zurichten von Leder und zur Textilbeschichtung |
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0570611A1 (de) * | 1992-05-20 | 1993-11-24 | Friedrich Maurer Söhne GmbH & Co. KG | Überbrückungskonstruktion für Dehnungsfugen |
WO2010108723A1 (de) | 2009-03-24 | 2010-09-30 | Evonik Degussa Gmbh | Prepregs und daraus bei niedriger temperatur hergestellte formkörper |
DE102009001806A1 (de) | 2009-03-24 | 2010-09-30 | Evonik Degussa Gmbh | Prepregs und daraus bei niedriger Temperatur hergestellte Formkörper |
WO2010108701A1 (de) | 2009-03-24 | 2010-09-30 | Evonik Degussa Gmbh | Prepregs und daraus hergestellte formkörper |
DE102009001793A1 (de) | 2009-03-24 | 2010-10-07 | Evonik Degussa Gmbh | Prepregs und daraus hergestellte Formkörper |
DE102010029355A1 (de) | 2010-05-27 | 2011-12-01 | Evonik Degussa Gmbh | Verfahren zur Herstellung von lagerstabilen Polyurethan-Prepregs und daraus hergestellte Formkörper |
WO2011147688A1 (de) | 2010-05-27 | 2011-12-01 | Evonik Degussa Gmbh | Verfahren zur herstellung von lagerstabilen polyurethan-prepregs und daraus hergestellte formkörper |
DE102010041247A1 (de) | 2010-09-23 | 2012-03-29 | Evonik Degussa Gmbh | Verfahren zur Herstellung von lagerstabilen Polyurethan-Prepregs und daraus hergestellte Formkörper aus Polyurethanzusammensetzung in Lösung |
WO2012038105A1 (de) | 2010-09-23 | 2012-03-29 | Evonik Degussa Gmbh | Verfahren zur herstellung von lagerstabilen polyurethan-prepregs und daraus hergestellte formkörper aus polyurethanzusammensetzung in lösung |
WO2012093006A1 (de) | 2011-01-04 | 2012-07-12 | Evonik Degussa Gmbh | Composite-halbzeuge und daraus hergestellte formteile sowie direkt hergestellte formteile auf basis von hydroxyfunktionalisierten (meth) acrylaten, die mittels uretdionen duroplastisch vernetzt werden |
DE102011006163A1 (de) | 2011-03-25 | 2012-09-27 | Evonik Degussa Gmbh | Lagerstabile Polyurethan-Prepregs und daraus hergestellte Formkörper aus Polyurethanzusammensetzung mit flüssigen Harzkomponenten |
WO2012130672A1 (de) | 2011-03-25 | 2012-10-04 | Evonik Degussa Gmbh | Lagerstabile polyurethan-prepregs und daraus hergestellte formkörper aus polyurethanzusammensetzung mit flüssigen harzkomponenten |
DE102011087226A1 (de) | 2011-11-28 | 2013-05-29 | Evonik Degussa Gmbh | Pseudo-thermoplastische, selbstvernetzende Composites |
WO2013079286A1 (de) | 2011-11-28 | 2013-06-06 | Evonik Degussa Gmbh | Pseudo-thermoplastische, selbstvernetzende composites |
DE102013204124A1 (de) | 2013-03-11 | 2014-09-11 | Evonik Industries Ag | Composite-Halbzeuge und daraus hergestellte Formteile sowie direkt hergestellte Formteile auf Basis von hydroxyfunktionalisierten (Meth)Acrylaten und Uretdionen die mittels Strahlung duroplastisch vernetzt werden |
WO2014139796A1 (de) | 2013-03-11 | 2014-09-18 | Evonik Industries Ag | Composite-halbzeuge und daraus hergestellte formteile sowie direkt hergestellte formteile auf basis von hydroxyfunktionalisierten (meth)acrylaten und uretdionen die mittels strahlung duroplastisch vernetzt werden |
WO2015074887A1 (de) | 2013-11-19 | 2015-05-28 | Evonik Industries Ag | Formteile auf basis von dien-funktionalisierten (meth)acrylaten und (hetero-)diels-alder-dienophilen, mit reversibler vernetzung |
US9550313B2 (en) | 2014-04-25 | 2017-01-24 | Evonik Degussa Gmbh | Process for the production of storage-stable epoxy prepregs, and composites produced therefrom, based on epoxides and acids amenable to free-radical polymerisation |
DE102014207785A1 (de) | 2014-04-25 | 2015-10-29 | Evonik Degussa Gmbh | Verfahren zur Herstellung von lagerstabilen Epoxy-Prepregs und daraus hergestellte Composites auf Basis von radikalisch polymerisierbaren Säuren und Epoxiden |
EP2940069A1 (de) | 2014-04-25 | 2015-11-04 | Evonik Degussa GmbH | Verfahren zur herstellung von lagerstabilen epoxy-prepregs und daraus hergestellte composites auf basis von radikalisch polymerisierbaren säuren und epoxiden |
EP2979851A1 (de) | 2014-07-28 | 2016-02-03 | Evonik Degussa GmbH | Effiziente Herstellung von Composite-Halbzeugen und -Bauteilen im Nasspressverfahren unter Einsatz von hydroxyfunktionalisierten (Meth) Acrylaten, die mittels Isocyanaten oder Uretdionen duroplastisch vernetzt werden |
WO2016016069A1 (de) | 2014-07-28 | 2016-02-04 | Evonik Degussa Gmbh | Effiziente herstellung von composite-halbzeugen und -bauteilen im nasspressverfahren unter einsatz von hydroxyfunktionalisierten (meth) acrylaten, die mittels isocyanaten oder uretdionen duroplastisch vernetzt werden |
EP2982704A1 (de) | 2014-08-06 | 2016-02-10 | Evonik Degussa GmbH | Reversibel vernetzte Polymeremulsionen |
EP2993202A1 (de) | 2014-09-08 | 2016-03-09 | Evonik Degussa GmbH | Composite-Halbzeuge und daraus hergestellte Formteile sowie direkt hergestellte Formteile auf Basis von hydroxyfunktionalisierten (Meth)Acrylaten und Uretdionen, die duroplastisch vernetzt werden |
EP3199575A1 (de) | 2016-01-29 | 2017-08-02 | Evonik Degussa GmbH | Neuartiger hetero-diels-alder-vernetzer und deren verwendung in reversibel vernetzenden polymersystemen |
WO2017129483A1 (de) | 2016-01-29 | 2017-08-03 | Evonik Degussa Gmbh | Neuartiger hetero-diels-alder-vernetzer und deren verwendung in reversibel vernetzenden polymersystemen |
EP3296347A1 (de) | 2016-09-20 | 2018-03-21 | Evonik Degussa GmbH | Neuartiger dien-baustein für die verwendung in reversibel vernetzenden (hetero-)diels-alder-polymersystemen |
WO2018054684A1 (de) | 2016-09-20 | 2018-03-29 | Evonik Degussa Gmbh | Neuartiger vernetzer-baustein für die verwendung in reversibel vernetzenden polymersystemen |
EP3330311A1 (de) | 2016-12-02 | 2018-06-06 | Evonik Degussa GmbH | Lagerstabile 1k-polyurethan-prepregs und daraus hergestellte formkörper aus polyurethanzusammensetzung |
US10626236B2 (en) | 2016-12-02 | 2020-04-21 | Evonik Operations Gmbh | Storage-stable one-component polyurethane prepregs and shaped bodies composed of polyurethane composition that have been produced therefrom |
EP3560971A1 (de) | 2018-04-27 | 2019-10-30 | Evonik Degussa GmbH | Zweikomponentige hybrid-matrix-system aus polyurethanen und polymethacrylaten zur herstellung von kurzfaserverstärkten halbzeugen |
Also Published As
Publication number | Publication date |
---|---|
US4812521A (en) | 1989-03-14 |
EP0309221A3 (de) | 1990-04-18 |
CA1337092C (en) | 1995-09-19 |
AU601930B2 (en) | 1990-09-20 |
JPH01108251A (ja) | 1989-04-25 |
AU2241288A (en) | 1989-03-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4812521A (en) | Epoxy resins modified with N-R-[(oxy or thio)methyl]acrylamide terpolymers | |
US3947522A (en) | Epoxy resin compositions | |
US3974129A (en) | Polybutadiene resin | |
EP0152425B1 (de) | Stabile dispersionen organischer polymere in polyepoxyden | |
US4708996A (en) | Stable dispersions of polymers in polyepoxides | |
DE2453874A1 (de) | Klebstoffzusammensetzungen | |
US4939271A (en) | Mercapto-modified N-(R-oxymethyl) acrylamide/rubber-formable monomer/(meth)acrylonitrile terpolymers | |
US4565853A (en) | Compositions for forming epoxy adhesive containing acrylate rubber | |
US4789712A (en) | Stable dispersions of polymers in polyepoxides | |
US4350789A (en) | Polyester resins toughened with vinyl terminated liquid polymers | |
DE2727417A1 (de) | Verfahren zur herstellung von bindemitteln | |
DE69308309T2 (de) | Härtbare epoxy-vinylesterharz-zusammensetzung mit einem niedrigen exothermen höchstwert während des härtens | |
CA2055871A1 (en) | High impact resistance adhesive compositions | |
US3679707A (en) | Curing agent for epoxy resins | |
DE2411064A1 (de) | Mit butadienpolymeren modifizierte epoxyharze | |
KR920002772B1 (ko) | 아미드 개질된 에폭시 수지 | |
DE3828096A1 (de) | Alkenylphenol modifizierte polyimide | |
EP0072114B1 (de) | Härtbare ungesättigte Polyesterzusammensetzungen | |
US6143233A (en) | Polymers containing 2,3-dihydrofuran groups | |
EP0112391A1 (de) | Stabile wässrige dispersionen härtbarer harzzusammensetzungen und aus diesen hergestellte klebe- und beschichtungszusammensetzungen | |
GB1410111A (en) | Epoxy resin compositions containing n-alkyl substituted ethylenediamine curing agents | |
JPS61161248A (ja) | アクリルアミド系オリゴマ−およびその製法 | |
JP3370141B2 (ja) | エポキシ樹脂組成物およびその製造方法 | |
US3790633A (en) | Novel low-viscosity epoxy curing agents | |
JPS61197623A (ja) | 一液性エポキシ樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): DE FR GB IT SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): DE FR GB IT SE |
|
17P | Request for examination filed |
Effective date: 19901009 |
|
17Q | First examination report despatched |
Effective date: 19921006 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19950302 |